EP2303991A2 - Procédé pour éliminer des composés soufrés dans des carburants - Google Patents

Procédé pour éliminer des composés soufrés dans des carburants

Info

Publication number
EP2303991A2
EP2303991A2 EP09780144A EP09780144A EP2303991A2 EP 2303991 A2 EP2303991 A2 EP 2303991A2 EP 09780144 A EP09780144 A EP 09780144A EP 09780144 A EP09780144 A EP 09780144A EP 2303991 A2 EP2303991 A2 EP 2303991A2
Authority
EP
European Patent Office
Prior art keywords
sulfur
fuel
fuels
mof
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09780144A
Other languages
German (de)
English (en)
Inventor
Ingo Richter
Christoph Kiener
Itamar Michael Malkowsky
Sabine Achmann
Gunther Hagen
Martin Haemmerle
Ralf Moos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09780144A priority Critical patent/EP2303991A2/fr
Publication of EP2303991A2 publication Critical patent/EP2303991A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03

Definitions

  • the present invention relates to a process for the removal of sulfur-containing compounds from fuels, which comprises contacting a sulfur-containing fuel with copper-1,3,5-benzenetricarboxylic acid MOF.
  • the desulfurization of motor fuel is usually carried out in refineries with large-scale process in the production of fuels.
  • thermal, catalytic and hydrodesulfurization processes are also used.
  • catalytic processes based on microbiological processes are used. The former methods are carried out at high temperatures and pressures, so that they can be realized on board a motor vehicle hardly or only with great security.
  • Sulfur reduction in fuels is of great industrial interest both to meet regulatory requirements and in terms of sulfur compatibility of exhaust aftertreatment systems and fuel cells.
  • a legal framework for reducing the sulfur content of fuels is provided by the reduction of the sulfur content to 50 mg / kg of sulfur within the European Union in 2005.
  • all fuels with a sulfur content of more than 10 mg / kg have been charged with additional 1, 5 and per liter of mineral oil tax in Germany.
  • a new regulation even envisages the mandatory introduction of sulfur-free fuels from 01.01.2009, in order to implement the Directive of the European Parliament and of the Council on the quality of petrol and diesel fuels.
  • "Sulfur-free" in this sense means that a fuel sulfur content of up to 10 mg / kg can be present.
  • NOx storage catalysts or oxidation catalysts not to poison.
  • a possible exhaust gas purification concept envisages introducing into the exhaust gas system of a motor vehicle a NOx storage catalyst which can store nitrogen oxides for a certain time After this "storage phase” in which the catalyst is "filled” with the exhaust gas component to be stored, a desorption phase follows, in which the catalyst is "emptied".
  • the nitrate storage used are alkaline earth metal or alkali metal salts.
  • such compounds preferably react with the sulfur oxides also present in the exhaust gas, which form when the sulfur compounds present in the fuel are burned, to form alkali or alkaline-earth sulfates. After a certain period of operation, which depends on the concentration of sulfur Compounds in the fuel, therefore, such storage catalysts lose their storage capacity. They must be regenerated (also called “desulfated” or “desulfurized”). Methods of how such storage catalysts can be desulfurized, z. As described in EP 858 837, EP 860 595 or EP 899 430.
  • the engines are no longer operated during the regeneration phase in the normal above-described lean / rich alternating operation, but they are constantly operated fat and it must have a certain minimum temperature , which is needed for the desulfurization can be achieved. This method requires an increased fuel requirement. Furthermore, the NOx storage catalyst ages with each desulphurisation process.
  • the sulfur-reduced fuel thus leads to a better efficiency of the vehicle, since no fuel-consuming desulfurization procedures must be performed. In addition, the life of the catalysts increases.
  • sulfur-free fuel or highly desulfurized fuel increases the lifetime of fuel cells because sulfur, just as in the exhaust aftertreatment catalysts, poison the catalysts immobilized on the electrodes of the fuel cells.
  • the low-sulfur fuel is also used in diesel engines, where reducing the sulfur content of the diesel fuel can reduce particulate emissions in the exhaust gas.
  • EP 303 882 describes the removal of hydrogen sulfide with the aid of transition metal carboxylates.
  • carboxylates of titanium, vanadium, chromium, iron, cobalt, nickel, copper, zinc and / or manganese are mentioned.
  • carboxylates of 2- or 3-valent iron or 2-valent manganese are mentioned.
  • MOFs metal organic frameworks
  • MOF-5 Zn-terephthalic acid MOF
  • MoC x molybdenum or MoC x (10 wt .-%) doped (wt .-% 3).
  • a surface of greater than 2000 m 2 / g was achieved. Uptake of dibenzothiophene in a 35 ppmws feed was 2.5 mgS / g SO rbent.
  • WO 2005/63354 describes a process for the depletion of sulfur and / or sulfur-containing compounds from biochemically produced organic compounds such as bioethanol.
  • Zeolites are preferably used as adsorbers, but it is also possible to use organometallic frameworks.
  • organometallic frameworks no concrete MOF compounds are mentioned and no examples using MOFs are disclosed.
  • WO 2008/21194 describes the use of organometallic frameworks for the desulfurization of liquids, the organometallic frameworks being composed of chains of octahedral metal oxides which are linked via aromatic dicarboxylic acids.
  • Possible metals are aluminum, vanadium, chromium, iron, titanium, zirconium, hafnium and cerium.
  • WO 2006/125739 discloses the use of a suspension containing organometallic framework to reduce odor.
  • the odorous substances are, for example, sulfur or sulfur-containing compounds.
  • WO 2006/122920 describes the separation of odors from gases using organometallic frameworks. As gases are u. a. called sulfur compounds.
  • EP 1 702 925 discloses the suitability of porous organometallic framework material for receiving inadvertently spilled liquids, such as, for example, disinfectant, odorant, inorganic or organic solvent, fuel brake fluid or oil.
  • the present invention is therefore based on the object, the efficiency of the low-temperature process for the desulfurization of fuels in comparison to
  • the process should be suitable at atmospheric pressure for use in mobile systems.
  • the procedure should In addition to the desulphurisation of conventional fuels, they also offer a further reduction in the sulfur content of low-sulfur fuels.
  • the process plants for desulfurization should also take in the motor vehicle only a small volume and low additional weight and be integrated as directly as possible in the fuel supply system.
  • the maintenance of the desulfurization should be compatible with the usual maintenance intervals of the motor vehicle.
  • the inventive method is suitable for all commercial motor fuels, in particular gasoline, diesel, fuel oil, kerosene and / or methanol.
  • the process according to the invention is particularly suitable for the further desulfurization of already highly desulphurised petrol and diesel fuels.
  • the already desulphurized petrol and diesel fuels typically still have a residual sulfur content of 8 to 15 mg / kg.
  • the sulfur-containing compounds to be removed in the fuels are typically thiophene, carbon disulfide, hydrogen sulfide, thioether and / or thioesther.
  • the inventive method is advantageously carried out at a temperature of 0 to 100 0 C and at a pressure of 0.5 to 5 bar.
  • the method according to the invention is carried out at ambient temperature and ambient pressure, so that the method can advantageously be carried out on board a mobile system without further energy supply.
  • the sulfur uptake is advantageous during a reaction time, i. H. a residence time of 5 to 100 minutes, preferably 5 to 60 minutes, especially 45 to 60 minutes, largely completed.
  • Copper-1,3,5-benzenetricarboxylic acid MOF is advantageously used in a concentration of 5 mg / ml to 200 mg / ml, preferably 10 to 100 mg / ml, in particular 10 to 50 mg / ml, based on a sulfur content in the fuel of 8 mg / kg to 27 mg / kg used.
  • the sulfur content in the fuel is reduced by at least 30%, preferably at least 40%, more preferably at least 50% and in particular at least 60% based on the initial sulfur content with the aid of the process according to the invention.
  • the sulfur content in the fuel becomes a typical initial one
  • the sulfur content in the fuel is reduced by 10 to 30 mg / kg, preferably 15 to 30 mg / kg, in particular 20 to 30 mg / kg.
  • the sulfur uptake per gram of copper-1,3,5-benzenetricarboxylic acid MOF is at least 0.2 mg / g, preferably at least 0.25 mg / g, for example, the sulfur uptake is from 0.2 mg / g to 1 mg / g , preferably at 0.25 to 0.75 mg / g.
  • the sulfur uptake per gram of copper-1,3,5-benzenetricarboxylic acid MOF is advantageously 20 ⁇ g / g to 700 ⁇ g / g.
  • the sulfur content of the already desulfurized fuels is thus further reduced by at least 5%, preferably at least 10%, more preferably at least 15% and in particular at least 20% by means of the process according to the invention.
  • the sulfur content of already desulphurised fuels is reduced by 10 to 25% with the aid of the process according to the invention.
  • Copper-1,3,5-benzenetricarboxylic acid MOF is well known to those skilled in the art and is described, for example, in J. Mater. Chem. 2006, 16, 626-636. Meanwhile, copper-1, 3,5-benzenetricarboxylic acid MOF is commercially available.
  • these can also be prepared by electrochemical means. In this regard, reference is made to DE 103 55 087 and EP 1 687 462.
  • the organometallic frameworks prepared in this way have particularly good properties in connection with the adsorption and desorption of chemical substances, in particular of gases. They thus differ from those produced conventionally, even if they are formed from the same organic and metal ion constituents. and are therefore to be considered as new framework materials.
  • electrochemically prepared organometallic frameworks are particularly preferred.
  • the copper-1,3,5-benzenetricarboxylic acid MOF may be used in admixture with other MOFs.
  • the copper-1,3,5-benzenetricarboxylic acid MOF may further be admixed with all auxiliaries and additives known to the person skilled in the art.
  • the copper-1,3,5-benzenetricarboxylic acid MOF can be used in powder form or as a shaped body. There are essentially no limitations on the possible geometries of these copper-1,3,5-benzenetricarboxylic acid MOF shaped bodies. For example, pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycomb, mesh or hollow body may be mentioned. The production of the moldings can be carried out by all methods known to the person skilled in the art, as described, for example, in DE 10 2005 012 087 on page 20 et seq.
  • the copper-1,3,5-benzenetricarboxylic MOF can also be applied to a support to ensure optimum accessibility of all active surfaces of the MOF.
  • Suitable supports are any of those known to those skilled in the art, for example alumina based supports, ceramic supports (e.g., Korderite), metallic supports (e.g., steel sheet honeycomb or aluminum-chromium high temperature sheet), or polymeric supports.
  • the method can advantageously be used directly on board a mobile system, in particular a motor vehicle, and thus reduce the sulfur content of commercially available fuels in situ or limit it to a predetermined maximum.
  • Copper-1,3,5-benzenetricarboxylic acid MOF can advantageously be structurally integrated into the fuel filter.
  • the copper-1,3,5-benzenetricarboxylic acid MOF can be present, for example, layered with the filter material or structurally arranged directly before or after the filter material.
  • the copper-1, 3,5-benzenetricarboxylic acid MOF can be advantageously used as a disposable recyclable device, for example, the consumer himself before the refueling process can be introduced and is available for example at gas stations.
  • the inventive method is carried out continuously, so that the desulfurized fuel is supplied to the engine without intermediate storage.
  • a sulfur sensor can be integrated on board the motor vehicle, which monitors the sulfur content of the motor vehicle. By integrating the amount of fuel consumed, it is possible to conclude on the amount of sulfur introduced into the catalytic converter. The time of a required desulfurization can thus be calculated exactly.
  • Another application of the low-sulfur fuel is the use in the desulfurization of a catalyst in the exhaust aftertreatment system of an engine.
  • the low-sulfur fuel can also be used as a reducing agent for exhaust catalysts in the lean exhaust gas.
  • the advantage of the present invention for the desulfurization of fuels is that the low-sulfur or sulfur-free fuel in the fuel tank is available and thus can be fed directly to the engine when starting. By using the obtained sulfur-reduced fuel, the life of the exhaust aftertreatment systems can be significantly extended.
  • FIG. 3 shows the time-dependent desulfurization of model oils by adding copper-1,3,5-benzenetricarboxylic MOF (Cu-BTC-MOF)
  • FIG. 5 Dependence of Desulfurization on the MOF Material Used
  • FIG. 6 to FIG. 9 each show advantageous structures for carrying out the method according to the invention.
  • 1 shows a test setup for determining the adsorber properties of the Cu-BTC-MOF:
  • a certain concentration of the adsorber material 2 was weighed into a closed vessel 1 filled with fuel or model oil.
  • the continuous, circular motions of a vortexer 3 ensured uniform contact with the entire surface of the adsorber material.
  • the fuel was removed from the vessel and purified via two filtration units 4-5 so that no residues of the adsorbent material remained in the filtrate and the desulfurized fuel could be fed directly to the analysis 6.
  • the filtrate was fed offline to an elemental analyzer.
  • the filter residue ie the adsorbent material enriched with sulfur components, was dried and was then available for solid-state analysis or regeneration experiments.
  • FIG. 2 illustrates the dependence of the desulphurization of a thiophene-containing model oil on the loading of the adsorber container with adsorption material.
  • the model oil consisted of a thiophene-containing dodecane solution with a total sulfur content of 27 mg / kg.
  • 12.5 mg / ml or 50 mg / ml Cu-BTC-MOF it was possible to achieve an adsorber concentration-dependent sulfur reduction to 16.2 mg / kg or 7.7 mg / kg.
  • the sulfur uptake was 0.67 mg / g for 12.5 mg / ml Cu-BTC-MOF or 0.29 mg / g for 50 mg / ml Cu-BTC-MOF ( Figure 2a).
  • the model oil consisted of a thiophene-containing dodecane solution with a total sulfur content of 31 mg / kg.
  • a thiophene-containing dodecane solution with a total sulfur content of 31 mg / kg.
  • 50, 100 and 200 mg / ml Cu-BTC-MOF an adsorber concentration-dependent sulfur reduction to 13, 9 and 7 mg / kg was achieved.
  • the sulfur uptake was 0.4, 0.2 and 0.1 mg / g for 50, 100 and 200 mg / ml Cu-BTC-MOF ( Figure 2b).
  • FIG. 3 and FIG. 4 show time-resolved measurements of the time course of the sulfur reduction of a thiophene-containing model oil and an already low-sulfur real fuel:
  • Fig. 5 shows a comparison with the prior art and other MOF connections.
  • MOF compounds Zn-terephthalic acid MOF described by Thompson et al. selected support material, and on the other hand Cu-DABCO-terephthalic acid MOF and Cu-isophthalic acid MOF selected.
  • the model oil consisted of a thiophene-containing dodecan solution with a total sulfur content of 31 mg / kg.
  • the MOF compounds were each used in an amount of 50 mg / ml (6.6 wt%).
  • Figure 5 shows that Zn-terephthalic acid MOF and Cu-DABCO terephthalic acid MOF show no sulfur uptake.
  • Cu-isophthalic acid MOF shows only low sulfur uptake.
  • the sulfur content could only be reduced to 25.5 mg / kg, which corresponds to a decomposition rate of 0.05 mg / g (ms / rriMOF).
  • the sulfur content was reduced to 11 mg / kg, which corresponds to a decomposition rate of 0.28 mg / g (ms / rriMOF).
  • FIGS. 6 to 9 sketches of advantageous constructions illustrate the possible use of the adsorbent material directly on board the motor vehicle:
  • the adsorbent material 7 is integrated into the fuel filter 8 and arranged in series behind the filter material 9.
  • An electric fuel pump 10 pumps the fuel from the tank 11 via the adsorber filter unit 8 before being injected into the engine 12.
  • the adsorbent material 7 is arranged to fill the volume of the filter material, so that the replacement of only one unit would be possible.
  • the fuel first flows into the interior of the adsorber filter unit 8 and from there via a permeable layer of filter material 9 and adsorber 7 in an outer region, before being injected into the engine.
  • the adsorber material 13 is integrated directly into the fuel tank 15 in a framework structure 14 which is permeable to the fuel.
  • the skeletal structure may consist of plates coated with the adsorber material as seen in FIG. 7A. The plates can be removed individually from the fuel tank for replacement.
  • the adsorber material is contained in a cartridge which can be removed from the tank as needed. The advantage of this construction is that, on average, the contact time of the adsorber material with the fuel to be desulphurized is considerably longer.
  • the adsorber material 16 is introduced into a pre-tank 17, which is filled during the refueling process. After desulfurization, the fuel enters the
  • Main tank 18 in which an optional sulfur sensor 19 monitors the instantaneous sulfur content.
  • the adsorber material 20 is located in a container which is connected behind the actual fuel tank 21 as a "refueling tank" 22.
  • An electric fuel pump 23 supplies fuel desulphurised from the refueling tank to the engine.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treating Waste Gases (AREA)

Abstract

La présente invention concerne un procédé pour éliminer des composés soufrés dans des carburants, caractérisé en ce qu'un carburant soufré est mis en contact avec un réseau métallo-organique (MOF) à base de cuivre et d'acide 1,3,5-benzène-tricarboxylique.
EP09780144A 2008-07-08 2009-07-03 Procédé pour éliminer des composés soufrés dans des carburants Withdrawn EP2303991A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09780144A EP2303991A2 (fr) 2008-07-08 2009-07-03 Procédé pour éliminer des composés soufrés dans des carburants

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08159910 2008-07-08
EP09780144A EP2303991A2 (fr) 2008-07-08 2009-07-03 Procédé pour éliminer des composés soufrés dans des carburants
PCT/EP2009/058425 WO2010003903A2 (fr) 2008-07-08 2009-07-03 Procédé pour éliminer des composés soufrés dans des carburants

Publications (1)

Publication Number Publication Date
EP2303991A2 true EP2303991A2 (fr) 2011-04-06

Family

ID=41507481

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09780144A Withdrawn EP2303991A2 (fr) 2008-07-08 2009-07-03 Procédé pour éliminer des composés soufrés dans des carburants

Country Status (3)

Country Link
US (1) US20110138781A1 (fr)
EP (1) EP2303991A2 (fr)
WO (1) WO2010003903A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE112011106150B4 (de) 2010-09-24 2023-09-28 Cummins Intellectual Property, Inc. Motorsteuersystem und Verfahren auf der Basis der Kraftstoffqualität
US9190114B1 (en) 2015-02-09 2015-11-17 Western Digital Technologies, Inc. Disk drive filter including fluorinated and non-fluorinated nanopourous organic framework materials
JP6406745B1 (ja) 2017-01-26 2018-10-17 パナソニック株式会社 脱硫装置および脱硫方法
US11242785B2 (en) * 2020-06-30 2022-02-08 Saudi Arabian Oil Company Process to capture SOx onboard vehicles and ships

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5974788A (en) * 1997-08-29 1999-11-02 Ford Global Technologies, Inc. Method and apparatus for desulfating a nox trap
DE10361508A1 (de) * 2003-12-23 2005-07-28 Basf Ag Verfahren zur Abreicherung von Schwefel und/oder schwefelhaltigen Verbindungen aus einer biochemisch hergestellten organischen Verbindung
DE102005022844A1 (de) * 2005-05-18 2006-11-23 Basf Ag Abtrennung von Geruchsstoffen aus Gasen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010003903A2 *

Also Published As

Publication number Publication date
WO2010003903A2 (fr) 2010-01-14
US20110138781A1 (en) 2011-06-16
WO2010003903A3 (fr) 2010-07-15

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